Hair dye composition

ABSTRACT

A hair dye composition containing a direct dye (1)                    
     wherein, R 1 , R 2  represents H or a lower alkyl group, A represents a group (2) or (3) and wherein B represents a group —Z 1 , —NR 8 —Z 1  or —CH=Z 2 .

TECHNICAL FIELD

The present invention relates to a hair dye composition featuringmarkedly high dyeing power, less color fade over time and a smallercolor tone change of the dye even after storage.

BACKGROUND ART

Hair dyes can be classified by the dye to be used therefor, or whetherthey have bleaching action of melanin or not. Typical examples include atwo-part permanent hair dye composed of a first part containing analkali agent, an oxidation dye and a direct dye such as nitro dye and asecond part containing an oxidizing agent; and one-part semi-permanenthair dye containing an organic acid or an alkali agent, and a direct dyesuch as acid dye, basic dye or nitro dye.

The above-described permanent hair dye is however accompanied with thedrawbacks that color tone imparted by an oxidation dye is not so vividand the color of the hair dyed with a vivid-color producing nitro dyeordinarily employed as a direct dye markedly fades over time and becomesdull soon even if the color tone rightly after dyeing is very vivid(Japanese Patent Application Laid-Open (Kokai) No. Hei 6-271435).

Recently, hair dyes containing as a direct dye a so-called cationic dyehaving a cation group contained in their conjugate system have beenreported (Japanese Language Laid-Open Publication (PCT) No. Hei8-507545, 8-501322 or 10-502946, or Japanese Patent ApplicationLaid-Open (Kokai) No. Hei 10-194942). They have been found to involvedrawbacks that intended dyeing effects are not available owing todecomposition of them caused by mixing, upon hair dyeing, with hydrogenperoxide ordinarily employed as an oxidizing agent; and that when thecation group is incorporated in an azo(—N═N)-based conjugated system,they are unstable to an alkali agent or a reducing agent essentiallycontained in a permanent hair dye.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a hair dye compositionfeaturing high hair dyeing power, less color fade over time andexcellent storage stability to permit only a smaller color tone changeof the dye after storage.

The present inventors have found that a hair composition containing acationic dye represented by the below-described formula (1) which isdisclosed as a dye for dyeing or printing fiber materials therewith inJapanese Patent Application Laid-Open (Kokai) No. Hei 7-166079, JapanesePatent Application Laid-Open (Kokai) No. Sho 54-111526, Japanese PatentApplication Laid-Open (Kokai) No. Sho 49-10215, Japanese PatentApplication Laid-Open (Kokai) No. Sho 48-923, Japanese PatentApplication Laid-Open (Kokai) No. Sho 56-76457, Japanese PatentApplication Laid-Open (Kokai) No. Sho 56-145952, Japanese PatentApplication Laid-Open (Kokai) No. Hei 7-3177, U.S. Pat. No. 4,600,776,Japanese Patent Application Laid-Open (Kokai) No. Hei 9-12914, GermanOffenlegungsschrift DE-3149047, German Offenlegungsschrift DE-3205647,Japanese Patent Publication No. Sho 51-35405, Japanese PatentPublication No. Sho 49-4531, Japanese Patent Publication No. Sho49-4530, Japanese Patent Application Laid-Open (Kokai) No. Sho 50-5683or Japanese Patent Application Laid-Open (Kokai) No. Sho 54-149731;which is known as C.I. 48010, C.I. 48015 (Basic Red 13), C.I. 48020(Basic Violet 7), C.I. 48030 (Basic Violet 21), C.I. 48035 (Basic Orange21), C.I. 48040 (Basic Orange 22), C.I. 48055 (Basic Yellow 11), C.I.48060 (Basic Yellow 21), C.I. 48065 (Basic Yellow 12), C.I. 48100 (BasicYellow 23), C.I. 48016 (Basic Red 14) or C.I. 48056(Basic Yellow 13); orwhich is described in “Liebigs Ann. Chem. 107-121(1981)” can dye thehair with high dyeing power without causing decomposition of the dyeupon hair dying, exhibits excellent light resistance, washingresistance, perspiration resistance, friction resistance and weatherresistance, and causes a smaller change in color tone of the dye afterstorage as compared with that rightly after preparation because the dyeexists in the composition stably.

In one aspect of the present invention, there is thus provided a hairdye composition comprising, as a direct dye, a compound represented bythe following formula (1):

[wherein, R¹ and R² each independently represents a hydrogen atom or aC₁₋₆ alkyl group which may have a substituent,

A represent a group of the following formula (2):

(in which, R³, R⁴ and R⁵ each independently represents a C₁₋₆ alkylgroup which may have a substituent, or R⁴ and R¹ may be coupled togetherto form a cyclic structure, and benzene ring a¹ may have a substituentother than a sulfonic acid group or may be condensed with an aromaticring), or a group of the following formula (3):

(in which, W represents an aralkyl group, a carbamoylalkyl group or agroup —T—NR⁶R⁷ (in which R⁶ and R⁷ each independently represents a C₁₋₆alkyl group which may have a substituent, an aromatic group which mayhave a substituent or a heterocyclic group which may have a substituent,or R⁶ and R⁷ may form a heterocyclic ring together with the adjacentnitrogen atom, and T represents a divalent linear C₁₋₄ hydrocarbon groupwhich may have a substituent), and pyridine ring a² may be condensedwith an aromatic ring),

B represents a group represented by the formula —Z¹, —NR⁸—Z¹ or —CH═Z²

(in which Z¹ represents an aromatic or heterocyclic aromatic group whichmay have a substituent, R⁸ represents a hydrogen atom, a C₁₋₄ alkylgroup which may have a substituent or an aromatic group which may have asubstituent or R⁸ and Z¹ may be coupled together to form anitrogen-containing heterocyclic group which may have a substituent, andZ² represents a divalent group obtained by removing two hydrogen atomsfrom the methylene group on the ring of a heterocyclic aromatic compoundwhich may have a substituent,

with the proviso that when A is a group of the formula (2), B representsthe group −Z¹, and Z¹ represents an aromatic group or, when A is a groupof the formula (2), B represents the group —CH═Z², Z² represents anindolinidene group and n does not stand for 0, the aromatic orindolinidene group has at least one substituent represented by theformula: —NR⁹R¹⁰ (in which R⁹ represents a C₁₋₄ alkyl group having as asubstituent a chlorine atom or a cyano, acylamino, alkoxy,monoalkylamino, dialkylamino or trimethylammoniumyl group, or a phenylgroup which may have a substituent and R¹⁰ represents a C₁₋₆ alkyl groupwhich may have a substituent),

n stands for an integer of 1 to 3 when B represents the group —Z¹ orgroup —NR⁸—Z¹ and n stands for an integer of 0 to 3 when B representsthe group —CH═Z²; and

Y³¹ represents an anion.

BEST MODE FOR CARRYING OUT THE INVENTION

In the formula (1), examples of the C₁₋₆ alkyl group represented by R¹or R² include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl,isobutyl and isopentyl groups. R¹ and R² may be the same or different.Examples of the substituent which may be possessed by them include cyanogroup, chlorine atom, hydroxyl group, amino group, methoxy group anddiethylamino group. When B stands for the group —Z¹ or —NR⁸—Z¹,particularly preferred as n is 1, while when B stands for the group—CH═Z², 0 or 1 is particularly preferred. When B stands for the group—CH═Z², 0 is most preferred as n because of stability to an oxidizingagent, particularly to hydrogen peroxide.

In the formula (1), when A represents a group of the formula (2),examples of the C₁₋₆ alkyl group represented by R³, R⁴ or R⁵ includemethyl ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl andisopentyl groups. R³, R⁴ and R⁵ may be the same or different. R⁴ and R¹may form a cyclic structure together with two adjacent carbon atoms andas such a cyclic structure, 5— to 7-membered ones are preferred. R³, R⁴or R⁵ may have, as a substituent, a sulfonic acid group or salt thereof,cyano group, chlorine atom, hydroxyl group, amino group, alkoxy group,monoalkylamino group, dialkylamino group, trimethylammoniumyl group, oxogroup, carbamoyl group, carboxy group or aryl group.

Examples of the substituent which may be possessed by benzene ring a¹ inthe formula (2) include C₁₋₆ alkyl groups which may be substituted witha hydroxyl group, C₁₋₆ alkoxy groups, halogen atoms, C₂₋₇ alkoxycarbonylgroups, carboxy group or salts thereof, C₁₋₆ acylamino groups, aminogroup which may be substituted with one or two C₁₋₆ alkyl groups whichmay be substituted with a hydroxyl group, nitro group, hydroxyl group,and C₁₋₆ acyl groups. This a¹ may be cyclocondensed with an aromaticring and a naphthalene ring may be mentioned as such a condensed ring.

In the formula (1), when A is the group (3), examples of the aralkylgroup represented by W include benzyl, 1-phenethyl and 2-phenethylgroups, while those of the carbamoylalkyl group include carbamoylethyl.

In the formula (1), when A is the group (3) and W is the group —T—NR⁶R⁷,examples of the C₁₋₆ alkyl group represented by R⁶ or R⁷ include methyl,ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl and isopentylgroups, those of the aromatic group include phenyl and naphthyl, andthose of the heterocyclic group include imidazolyl and triazolyl. R⁶ andR⁷ may be the same or different, or the group —NR⁶R⁷ may be quaternized.In this group, R⁶ and R⁷ may form a heterocyclic ring, together with theadjacent nitrogen atom. As such a heterocyclic ring, pyrrolidine,piperidine, morpholine, piperazine, imidazole, triazole and pyridiniumrings may be mentioned by way of example. R⁶ or R⁷ may have asubstituent such as phenyl group, cyano group, chlorine atom, hydroxylgroup, amino group, methoxy group, diethylamino group or a group of thefollowing formula:

In the formula (3), the divalent linear C₁₋₄ hydrocarbon grouprepresented by T is, for example, a methylene, ethylene, trimethylene,tetramethylene or propylene group, with the ethylene or trimethylenegroup being particularly preferred. T may have, for example, a methyl,ethyl, phenyl, benzyl or hydroxyl group as a substituent.

In the formula (3), pyridine ring a² may be substituted with an aromaticring and examples of such a condensed heterocyclic ring includequinoline and isoquinoline rings.

In the formula (1), as a group represented by A, groups of the formula(2) are preferred because of stability to an oxidizing agent,particularly to hydrogen peroxide.

In the formula (1), B represents the group —Z¹, —NR⁸—Z¹ or —CH═Z².Examples of —Z¹ include groups of the following formulas:

These Z¹ may have, as a substituent, halogen atom, hydroxyl group, cyanogroup, C₁₋₈ alkyl group which may have a substituent, C₁₋₈ alkoxy groupwhich may have a substituent, amino group which may have a substituent,phenyl group which may have a substituent or a group of the formula:A—CH═CH—Z¹—D— (in which A and Z¹ have the same meanings as describedabove and D represents a group —NHCONH— or —NHCO—D′—CONH— (in which D′represents an alkylene, phenylene or naphthylene group)). When Z¹represents an aromatic group, it contains at least one —NR⁹R¹⁰.

Examples of the substituent for the alkyl or alkoxyl group which may besubstituted for Z¹ include cyano group, chlorine atom, dialkylaminogroup and trialkylammmoniumyl group. Examples of the substituent for theamino group which may be substituted for Z¹ include alkyl and arylgroups. These substituents may be substituted, for example, with an arylgroup, an alkoxy group, an alkyl group, a chlorine atom, a cyano group,an amino group, a monoalkylamino group, a dialkylamino group or atrialkylammoniumyl group.

As —Z¹, preferred are the following groups:

R⁸ is, for example, a hydrogen atom or a methyl, ethyl, propyl, butyl,phenyl, 4-hydroxyphenyl or 4-methoxyphenyl group.

As —CH═Z², following groups represented by the formula (5) or (6) can bementioned by way of example:

As a substituent which may be possessed by Z², C₁₋₆ alkyl groups and thelike can be mentioned. These alkyl groups may have a substituent similarto that exemplified as the substituent which may be possessed by R³, R⁴or R⁵. When Z² represents an indolinidene group and n does not stand for0, the indolinidene group have at least one group —NR⁹R¹⁰.

Among the compounds represented by the formula (1), preferred forstability to an oxidizing agent, particularly to hydrogen peroxide arethose wherein when A is represented by the formula (2), B is representedby a group of the formula —CH═Z², and n stands for 0, the group of theformula —CH═Z² is a group substituted, at a specific position of theformula (5) or (6), by an alkyl group, that is a group of the followingformula (7):

[wherein, R¹¹, R¹² and R¹³ each independently represents a C₁₋₆ alkylgroup which may have a substituent, and a benzene ring a³ may have asubstituent other than a sulfonic acid group or may be cyclocondensedwith an aromatic ring].

In short, compounds having a group of the formula (2) as A, a group ofthe formula (7) as B and 0 as n are most preferred for stability to anoxidizing agent, particularly to hydrogen peroxide. Such compounds (1)have the following formula (4):

[wherein, R³, R⁴, R⁵, R¹¹, R¹² and R¹³ each independently represents aC₁₋₆ alkyl group which may have a substituent; R¹⁴ and R¹⁵ eachindependently represents a hydrogen atom, a C₁₋₆ alkyl group which maybe substituted by a hydroxyl group, a C₁₋₆ alkoxy group, a halogen atom,a C₂₋₇ alkoxycarbonyl group, a carboxy group or salt thereof, a C₁₋₆acylamino group, an amino group which may be substituted with one or twoC₁₋₆ alkyl groups which may be substituted by a hydroxyl group, a nitrogroup, a hydroxyl group or a C₁₋₆ acyl group; benzene rings a¹ and a³may each be cyclocondensed with an aromatic ring; and Y represents ananion].

In the formula (4), examples of the C₁₋₆ alkyl group represented by R³,R⁴, R⁵, R¹¹, R¹² or R¹³ include methyl, ethyl, propyl, butyl, pentyl,hexyl, isopropyl, isobutyl and isopentyl groups. R³, R⁴, R⁵, R¹¹, R¹²and R¹³ may be the same or different. Examples of the substituent whichR³, R⁴, R⁵, R¹¹, R¹² or R¹³ may have include sulfonic acid group orsalts thereof, cyano group, chlorine atom, hydroxyl group, amino group,alkoxy groups, monoalkylamino groups, dialkylamino groups,trimethylammoniumyl group, oxo group, carbamoyl group, carboxy group andaryl groups.

As R¹⁴ or R¹⁵, examples of the C₁₋₆ alkyl group which may be substitutedby a hydroxyl group include, in addition to the above-exemplified C₁₋₆alkyl groups, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl,1-hydroxypropyl and 3-hydroxypropyl groups. Examples of the C₁₋₆ alkoxygroup represented by R¹⁴ or R¹⁵ include methoxy, ethoxy, propoxy,butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy and isopentyloxygroups. Examples of the halogen atom represented by R¹⁴ or R¹⁵ includefluorine, chlorine, bromine and iodine atoms. Examples of the C₂₋₇alkoxycarbonyl group represented by R¹⁴ or R¹⁵ include methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl,hexyloxycarbonyl, isopropoxycarbonyl, isobutoxycarbonyl andisopentyloxycarbonyl groups. Examples of the salt of a carboxy grouprepresented by R¹⁴ or R¹⁵ include ammonium salts, lithium salts, sodiumsalts and potassium salts. Examples of the C₁₋₆ acylamino grouprepresented by R¹⁴ or R¹⁵ include formamido, acetamido, propionamido,butanoylamino, pentanoylamino, hexanoylamino, isopropionamido,isobutanoylamino and isopentanoylamino groups. Examples of the aminogroup which may be substituted by one or two C₁₋₆ alkyl groups which maybe substituted by a hydroxyl group include amino, monomethylamino,dimethylamino, monoethylamino, diethylamino, monopropylamino,dipropylamino, mono(2-hydroxyethylamino, bis(2-hydroxyethyl)amino,mono(3-hydroxypropyl)amino, bis(3-hydroxypropyl)amino,mono(2-hydroxypropyl)amino, and bis(2-hydroxypropyl)amino groups.Examples of the C₁₋₆ acyl group represented by R¹⁴ or R¹⁵ includeformyl, acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, isopropanoyl,isobutanoyl and isopentanoyl groups.

In the formula (4), the benzene rings a¹ and a³ may each becyclocondensed with an aromatic ring and as such a condensed ring, anaphthalene ring may be mentioned as an example.

In the formulas (1) and (4), examples of the anion represented by Y⁻include chloride ions, bromide ions, iodide ions, trichlorozincic acidions, tetrachlorozincic acid ions, sulfuric acid ions, hydrogensulfateions, methyl sulfate ions, phosphoric acid ions, formic acid ions,acetic acid ions, perchloric acid ions and tetrafluoroboric acid ions.

The following are specific examples of the direct dye (1) to be used inthe present invention:

Compounds having a group of the formula (2) as A:

Among the direct dyes (1), those represented by the formula (4) can beprepared, for example, by the method described in “THE CHEMISTRY OFHETEROCYCLIC COMPOUNDS —THE CYANINE DYES AND RELATED COMPOUNDS—,54-55(1964)” or “Liebigs Ann. Chem., 107-121(1981)”.

As the direct dye (1), one or more of the above-exemplified compoundsmay be used. Alternatively, another direct dye can be used incombination.

Examples of the direct dye other than the direct dye (1) include BasicBlue 7 (C.I. 42595), Basic Blue 26 (C.I. 44045), Basic Blue 99 (C.I.56059), Basic Violet 10 (C.I. 45170), Basic Violet 14 (C.I. 42515),Basic Brown 16 (C.I. 12250), Basic Brown 17 (C.I. 12251), Basic Red 2(C.I. 50240), Basic Red 22 (C.I. 11055), Basic Red 76 (C.I. 12245),Basic Red 118 (C.I. 12251:1) and Basic Yellow 57(C.I. 12719); and basicdyes as described in Japanese Patent Publication No. Sho 58-2204,Japanese Patent Application Laid-Open No. Hei 9-118832, JapaneseLanguage Laid-Open Publication (PCT) No. Hei 8-501322 or JapaneseLanguage Laid-Open Publication (PCT) No. Hei 8-507545.

The direct dye (1) is preferably added in an amount of 0.01 to 20 wt. %,more preferably 0.05 to 10 wt. %, especially 0.1 to 5 wt. % on the basisof the entirety of the composition (after mixing of all the parts when atwo-part or three-part composition is employed; this will apply equallyhereinafter). When another direct dye is used in combination, thecontent of it with the direct dye (1) preferably ranges from 0.05 to 10wt. %, especially 0.1 to 5 wt. % based on the whole composition.

The hair dye composition of the present invention is preferably adjustedto pH 6 to 11, with pH 8 to 11 being more preferred. Examples of thealkali agent to be used for pH adjustment include ordinarily employedones such as ammonia, organic amines and salts thereof. The alkali agentis preferably added in an amount of 0.01 to 20 wt. %, more preferably0.1 to 10 wt. %, especially 0.5 to 5 wt. %.

In the hair dye composition of the present invention, an oxidizing agentcan be incorporated. In this case, hair dyeing and bleaching can becarried out simultaneously, which facilitates more vivid hair dyeing.Ordinarily employed oxidizing agents, for example, hydrogen peroxide,persulfates such as ammonium persulfate, potassium persulfate and sodiumpersulfate; perborates such as sodium perborate, percarbonates such assodium percarbonate and bromates such as sodium bromate and potassiumbromate are usable. Out of them, hydrogen peroxide is especiallypreferred. The oxidizing agent is added in an amount of 0.5 to 10 wt. %,especially 1 to 8 wt. %, on the basis of the entirety of thecomposition.

In the hair dye composition of the present invention, an oxidation dyecan be incorporated further. This incorporation enables remarkable vividdyeing not attainable by the single use of an oxidation dye. As theoxidizing agent, the above-exemplified ones can be used, with hydrogenperoxide being particularly preferred. Alternatively, an oxidizingenzyme such as laccase can be employed. For the oxidation dye, knowndevelopers and couplers ordinarily employed for an oxidation type hairdye can be used.

Examples of the developer include p-phenylenediamines having one orseveral groups selected from NH₂—, NHR— and NR₂— groups (R represents aC₁₋₄ alkyl or hydroxyalkyl group) such as p-phenylenediamine,p-toluylenediamine, N-methyl-p-phenylenediamine,chloro-p-phenylenediamine, 2-(2′-hydroxyethylamino)-5-aminotoluene,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine,methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine,2-chloro-6-methyl-p-phenylenediamine,6-methoxy-3-methyl-p-phenylenediamine, 2,5-diaminoanisole,N-(2-hydroxypropyl)-p-phenylenediamine andN-2-methoxyethyl-p-phenylenediamine; 2,5-diaminopyridine derivatives and4,5-diaminopyrazole derivatives; p-aminophenols such as p-aminophenol,2-methyl-4-aminophenol, N-methyl-p-aminophenol, 3-methyl-4-aminophenol,2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol,2,3-dimethyl-4-aminophenol and 2,5-dimethyl-4-aminophenol;o-aminophenols, o-phenylenediamines, 4,4′-diaminophenylamine andhydroxypropylbis(N-hydroxyethyl-p-phenylenediamine); and salts thereof.

Examples of the coupler include 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,5-amino-2-methylphenol, 5-(2′-hydroxyethylamino)-2-methylphenol,2,4-diaminoanisole, m-toluylenediamine, resorcin, m-phenylenediamine,m-aminophenol, 4-chlororesorcin, 2-methylresorcin,2,4-diaminophenoxyethanol, 2,6-diaminopyridine,2-amino-3-hydroxypyridine, 4-hydroxyindole, 6-hydroxyindole,2,4-diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine,2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine,4,6-diamino-2-hydroxypyrimidine and 1,3-bis(2,4-diaminophenoxy)propane;and salts thereof.

As a developer or coupler, at least one of the above-exemplified onescan be used. Although no particular limitation is imposed on itscontent, it is preferably added in an amount of 0.01 to 20 wt. %,especially 0.5 to 10 wt. % based on the whole composition.

To the hair dye composition of the present invention, a knownautoxidation dye typified by an indole or an indoline, or a known directdye such as a nitro dye or a disperse dye can also be added.

When an anionic component (such as anionic surfactant or anionicpolymer) is added to the hair dye composition of the present invention,it is preferred to satisfy the following equation:

 “Ion activity concentration of an anionic component/ion activityconcentration of a cationic direct dye (1)≦8”

The term “ion activity concentration” as used herein means “molarconcentration x ionic valence”

Addition of a polyol, polyol alkyl ether, cationic or amphoteric polymeror silicone to the hair dye composition of the present invention ispreferred, because the resulting composition can dye the hair uniformlyand has improved cosmetic effects.

In addition to the above-described components, those ordinarily employedas a raw material for cosmetics can be added to the hair dye compositionof the present invention. Examples of such an optional component includehydrocarbons, animal or vegetable fats and oils, higher fatty acids,organic solvents, penetration promoters, cationic surfactants, naturalor synthetic polymers, higher alcohols, ethers, amphoteric surfactants,nonionic surfactants, protein derivatives, amino acids, antiseptics,chelating agents, stabilizing agents, antioxidants, plant extracts,crude drug extracts, vitamins, colorants, perfumes and ultravioletabsorbers.

The hair dye composition of the present invention can be prepared in aconventional manner into a one-part composition, a two-part compositionhaving a first-part component containing an alkali agent and asecond-part component containing an oxidizing agent, or a three-partcomposition having, in addition to these two components, a powderyoxidizing agent such as persulfate. The direct dye (1) can beincorporated in either one or both of these components of the two-partor three-part composition. The one-part type is applied to the hairdirectly, while the two- or three-part type is applied to the hair aftermixing these parts upon hair dyeing.

No particular limitation is imposed on the form of the hair dyecomposition of the present invention. Examples include powder,transparent liquid, emulsion, cream, gel, paste, aerosol, and aerosolfoam. It preferably has a viscosity of 2000 to 100000 mPa·s in the stageof application to the hair (after mixing of all the components when atwo-part or three-part type composition is employed).

For dyeing the hair with the hair dye composition of the presentinvention, it is recommended to apply the hair dye composition of thepresent invention to the hair at 10 to 50° C. directly when it isone-part type and after mixing when it is two- or three-part type, allowit to act on the hair for 1 to 60 minutes, preferably 3 to 45 minutes,wash the resulting hair and then dry it.

EXAMPLES

Compounds employed in the below-described examples are as follows:

Examples 1 to 29

In a manner known per se in the art, hair dyes as shown in Tables 1 to 6were prepared. The hair was dyed by applying, to the hair at 30° C., adye directly when it was the dye shown in Table 1 or 3 and after mixingof components when it was the dye shown in Table 2, 4, 5 or 6, allowingto act it on the hair for 30 minutes, washing the resulting hair anddrying.

Any dye composition of Examples 1 to 29 showed markedly high hair dyeingpower, excellent light resistance, washing resistance, frictionresistance and heat resistance and had a smaller change in color shadeof the dye after storage.

TABLE 1 Example Component (wt. %) 1 2 3 4 5 6 Foam Compound (a) 0.5 0.30.3 Compound (k) 0.5 0.3 0.3 Basic Red 76 — — 0.1 — — 0.1 HC Red 3 — 0.2— — 0.2 — Monoethanolamine 1 1 1 1 1 1 Ethanol 15 15 15 15 15 15Propylene glycol 10 10 10 10 10 10 Polyoxyethylene (20) octyldodecylether 10 10 10 10 10 10 Polyoxyethylene (9) tridecyl ether 3 3 3 3 3 3Polyoxyethylene (3) tridecyl ether 6 6 6 6 6 6 Diethanolamide oleate 8 88 8 8 8 Oleyl alcohol 2 2 2 2 2 2 Ammonium chloride q.s. *1 q.s. *1 q.s.*1 q.s. *1 q.s. *1 q.s. *1 LPG (4.0 kg · cm) 10 10 10 10 10 10 Purifiedwater Bal- Bal- Bal- Bal- Bal- Bal- ance ance ance ance ance ance *1:amount to adjust pH to 8.5

TABLE 2 Example Component (wt. %) 7 8 9 10 First part Compound (b) 0.50.3 0.3 0.3 Basic Red 76 — — — 0.1 HC Red 3 — 0.2 — — p-Aminophenol — —0.2 0.2 p-Amino-o-cresol — — 0.2 0.2 Ammonia (28%) 6 6 6 6 Ethanol 15 15— — Propylene glycol 10 10 2 2 Polyoxyethylene (20) octyldodecyl ether10 10 — — Polyoxyethylene (40) cetyl ether — — 2 2 Polyoxyethylene (2)cetyl ether — — 2.5 2.5 Diethanolamide oleate 8 8 — — Oleyl alcohol 2 2— — Stearyl trimethylammonium chloride — — 1.5 1.5 Cetanol — — 1.0 1.0Liquid paraffin — — 0.5 0.5 Ammonium chloride q.s. *2 q.s. *2 q.s. *2q.s. *2 Sodium sulfite 0.5 0.5 0.5 0.5 Tetrasodiumethylenediaminetetraacetate 0.1 0.1 0.1 0.1 Purified water BalanceBalance Balance Balance Second Hydrogen peroxide 6 6 6 6 part Methyparaben 0.1 0.1 0.1 0.1 Phosphoric acid q.s. *3 q.s. *3 q.s. *3 q.s. *3Purified water Balance Balance Balance Balance Third part Ammoniumpersulfate (powder) — 2 — — *2: amount to adjust pH to 9.8, *3: amountto adjust pH to 3.5

TABLE 3 Example Component (wt. %) 11 12 13 14 15 Dye [Compound (e)] 0.20.15 0.1 0.2 Dye [Compound (i)] 0.5 0.1 Dye [Compound (d)] 0.5 0.1 0.2Dye [Compound (α), red] 0.15 0.05 Dye [Compound (β), yellow] 0.1 0.1Ethanol 5 5 5 Propylene glycol 5 5 Diethylene glycol monoethyl ether 10Guar gum 1 Hydroxypropyl guar gum 1 1 1 1 “Gufquat 734” (trade name;product of 1 1 ISP Japan) “Catinal LC100” (trade name; product of 1 1Toho Chemical Industry) “Polyether-modified silicone KF6005” 0.4 tradename; (product of Shin-Etsu Chemical) “Amodimethicone SM8702C” (productof 1.5 Dow Corning Toray Silicone) Monoethanolamine 0.1 Phosphoric acidAmount to adjust pH to 9 Perfume q.s. Water Balance Total (g) 100

TABLE 4 Example Component (wt. %) 16 17 18 19 20 21 1st Dye [Compound(j)] 0.2 0.15 0.2 part Dye [Compound (f)] 0.1 0.15 Dye [Compound (k)]0.4 0.3 Dye [Compound (α), red] 0.1 0.05 0.1 28 wt. % aqueous ammonia 5Monoethanolamine 2 Propylene glycol 8 Polyoxyethylene (20) isostearyl 24ether Polyoxyethylene (2) isosteary 20 ether “Merquat 280” (trade name;8 8 product of Calgon Corp., 35 wt. % aqueous solution) “Polymer JR400”(trade name; 0.5 0.5 0.5 product of Union Carbide) “AmodimethiconeSM8702C” 2 (trade name; product of Dow Corning Toray Silicone)“Polyether modified silicone 0.3 0.3 KF6005” (trade name; product ofShin-Etsu Chemical) Tetrasodium 0.1 ethylenediaminetetraacetate Perfumeq.s. Ammonium chloride Amount to adjust pH to 10 Water Balance 2nd 35wt. % aqueous hydrogen 17.1 part peroxide Methylparaben 0.1 Phosphoricacid Amount to adjust pH to 3.5 Water Balance

TABLE 5 Example Component (wt. %) 22 23 24 25 26 27 1stToluee-2,5-diamine 1.9 1 1.9 1 part Para-aminophenol 1 1 Resorcin 2 2Para-amino-ortho-cresol 1.1 1.1 2,4- 1.37 1.37 Diaminophenoxyethanol Dye[Compound (g)] 0.05 0.05 Dye [Compound (c)] 0.15 Dye [Compound (h)] 0.1Dye [Compound (k)] 0.3 0.1 0.2 28 wt. % aqueous ammonia 5Monoethanolamine 2 Propylene glycol 8 Polyoxyethylene (20) 24 isostearylether Polyoxyethylene (2) 20 isostearyl ether “Merquat 280” (trade 8 8name; product of Calgon Corp., a 35 wt. % aqueous solution) “PolymerJR400” (product 0.5 0.5 of Union Carbide) “Amodimethicone 2 2 SM8702C”(trade name; product of Dow Corning Toray Silicone) Sodium sulfite 0.05Ascorbic acid 0.5 Tetrasodium 0.1 ethylenediaminetetraacetate Perfumeq.s. Ammonium chloride Amount to adjust pH to 10 Water Balance 2nd 35wt. % Aqueous 17.1 part hydrogen peroxide Methylparaben 0.1 Phosphoricacid Amount to adjust pH to 3.5 Water Balance

TABLE 6 Examples Component (wt. %) 28 29 First part P-aminophenol 1P-amino-o-cresol 1.1 Compound (i) 0.1 Compound (a) 0.2 28 wt. % aqueousammonia 5 Monoethanolamine 2 Cetanol 8.5 Polyoxyethylene (40) cetylether 3 Polyoxyethylene (2) cetyl ether 3.5 Stearyl trimethyl ammoniumchloride 2 Liquid paraffin 0.5 Sodium sulfite 0.05 Ascorbic acid 0.5Tetrasodium ethylenediaminetetraacetate 0.1 Perfume q.s. Ammoniumchloride Amount to adjust pH to 10 Water Balance Second part 35 wt. %aqueous hydrogen peroxide 17.1 Methylparaben 0.1 Phosphoric acid Amountto adjust pH to 3.5 Water Balance

What is claimed is:
 1. A hair dye composition comprising, a direct dyecompound of formula (1):

wherein, R¹ and R² each independently represent a hydrogen atom or aC₁₋₆ alkyl group which may have a substituent; A represents a group offormula (2):

 wherein R³, R⁴ and R⁵ each independently represent a C₁₋₆ alkyl groupwhich may have a substituent, or R⁴ and R⁵ may be coupled together toform a cyclic structure, benzene ring a¹ may have a substituent otherthan a sulfonic acid group or may be condensed with an aromatic ring, orA is a group of formula (3):

 wherein W represents an aralkyl group, a carbamoylalkyl group or—T—NR⁶R⁷, wherein R⁶ and R⁷ each independently represent a C₁₋₆ alkylgroup which may have a substituent, an aromatic group which may have asubstituent or a heterocyclic group which may have a substituent, or R⁶and R⁷ may form a heterocyclic ring together with the adjacent nitrogenatom, and T represents a divalent linear C₁₋₄ hydrocarbon group whichmay have a substituent, pyridine ring a² may be condensed with anaromatic ring, B represents a group represented by the formula —Z¹,—NR⁸—Z¹ or —CH═Z² wherein when A is a group of formula (3) Z¹ representsan aromatic or heterocyclic aromatic group which may have a substituent,R⁸ represents a hydrogen atom, a C₁₋₄ alkyl group which may have asubstituent or an aromatic group which may have a substituent or R⁸ andZ¹ may be coupled together to form a nitrogen-containing heterocyclicgroup which may have a substituent, Z² represents a divalent groupobtained by removing two hydrogen atoms from the methylene group on thering of a heterocyclic aromatic compound which may have a substituent,wherein when A is a group of formula (2) R⁸ represents a hydrogen atom,a C₁₋₄ alkyl group which may have a substituent or an aromatic groupwhich may have a substituent or R⁸ and Z¹ may be coupled together toform a nitrogen-containing heterocyclic group which may have asubstituent, Z² represents a divalent group obtained by removing twohydrogen atoms from the methylene group on the ring of a heterocyclicaromatic compound which may have a substituent, and Z¹ may have asubstituent and is selected from the group consisting of

with the proviso that when A is a group of formula (2), B represents thegroup —Z¹ and Z¹ represents an aromatic group or when A is a group offormula (2), B represents the group —CH═Z², Z² represents anindolinidene group and n does not stand for 0, the aromatic group orindolinidene group has at least one substituent represented by theformula: —NR⁹R¹⁰ wherein R⁹ represents a C₁₋₄ alkyl group having as asubstituent a chlorine atom or a cyano, an acylamino, an alkoxy, amonoalkylamino, a dialkylamino, a trimethylammoniumyl group, or a phenylgroup which may have a substituent and R¹⁰ represents a C₁₋₆ alkyl groupwhich may have a substituent, n stands for an integer of 0 to 3, whereinwhen B represents the group —Z¹ or group —NR⁸—Z¹ n is 1 to 3 and when Brepresents the group —CH═Z² n is 0 to 3; and Y³¹ stands for an anion. 2.The hair dye composition according to claim 1, further comprising anoxidizing agent.
 3. The hair dye composition according to claim 1,further comprising an oxidation dye.
 4. The hair dye compositionaccording to claim 1, wherein A in formula (1) represents a group offormula (2).
 5. The hair dye composition according to claim 1, whereinthe compound of formula (1) is represented by formula (4):

wherein, R³, R⁴, R⁵, R¹¹, R¹² and R¹³ each independently represent aC₁₋₆ alkyl group which may have a substituent; R¹⁴ and R¹⁵ eachindependently represent a hydrogen atom, a C₁₋₆ alkyl group which may besubstituted by a hydroxyl group, a C₁₋₆ alkoxy group, a halogen atom, aC₂₋₇ alkoxycarbonyl group, a carboxy group or salt thereof, a C₁₋₆acylamino group, an amino group which may be substituted with one or twoC₁₋₆ alkyl groups which may be substituted by a hydroxyl group, a nitrogroup, a hydroxyl group or a C₁₋₆ acyl group; benzene rings a¹ and a³may each be cyclocondensed with an aromatic ring; and Y⁻ represents ananion.
 6. A method for dyeing the hair comprising applying the hair dyecomposition of claim 1 to the hair; allowing the hair dye composition toact on the hair for a time and under conditions suitable for dying;removing the hair dye composition from the hair.
 7. The hair dyecomposition according to claim 1, wherein R⁶ or R⁷ may be a group of:


8. The hair dye composition according to claim 2, wherein the oxidizingagent is selected from the group consisting of hydrogen peroxide,ammonium persulfate, potassium persulfate, sodium persulfate, sodiumperborate, sodium percarbonate, sodium bromate, and potassium bromate.9. The hair dye composition according to claim 2, wherein the oxidizingagent comprises 0.5 to 10% by weight of the total composition.
 10. Thehair dye composition according to claim 3, wherein the oxidation dyecomprises 0.01 to 20% by weight of the total composition.
 11. The hairdye composition according to claim 1, wherein the direct dye comprises0.01 to 20% by weight of the total composition.
 12. The hair dyecomposition according to claim 1, further comprising an alkali agent.13. The hair dye composition according to claim 1, wherein the alkaliagent comprises 0.02 to 20% by weight of the total composition.
 14. Thehair dye composition according to claim 1, further comprising anautoxidation dye, a nitro dye, or a disperse dye.
 15. The hair dyecomposition according to claim 1, further comprising an anionicsurfactant or an anionic polymer.
 16. The hair dye composition accordingto claim 1, further comprising a polyol, a polyol alkyl ether, acationic polymer, a amphoteric polymer, or silicone.
 17. A hair dyecomposition comprising, a direct dye compound selected from the groupconsisting of


18. A hair dye composition comprising, a direct dye compound selectedfrom the group consisting of


19. The method according to claim 6, wherein the time is 1 to 60minutes.
 20. The method according to claim 6, wherein the conditionssuitable for dying is a temperature of 10 to 50° C.